Process for the production of sulpho-acids from hydrocarbon oils



Pd'tented June 3, 1930' UNITED STATES PATENT OFFICE- .em'eonr rnrnorr, or MOSCOW, nussrannn PETER sn'nsmnorr, or rams, rmcn,

ASSIGNORS TO THE FIRST NATIONAL BANK, OF CINCINNATL'OHIO .raocnss non THE ra'onuc'rion or SULPHO-ACIDS mom mnocnnnon one No Drawing. Application filed Deeember' 30, 1925, Serial No. 78,486, and in Germany January 28, 1925.

. This invention relates to processes for the production of sulpho-acids from hydrocarbons and it comprises a process in which a hydrocarbon oil which may no longer be sulfonated is oxidized with air to dehydrogenate the oil and the oxidized mixture thereafter sulfonated with sulphuric acid.

In the sulfonation of crude petroleum hydrocarbons'such as naphtha, naphtha distilally prepared late, etc., sulfonation maybe carried out up to a certain point beyond which no more sulfonation takes place, even though the sulfonating mixture is heated to temperatures of 100 C. @n this fact is based the process for the production of the. so callediwhite oils, which are both odorless and tasteless and are ,known under the name of parafinum liquidum, or liquid )arafline. These oils are usuy sulfon'atin'g heavy solar, spindle, or machine oil distillates by means of 40 to 50% fuming sulphuric acid. ;A yield of 50 to 6 0%- .of white oils are obtained which consist of a mixture of hydrocarbons. Further sulfonation of these hydrocarbons is very ditficult to bring about.

The object of the present invention is to devise a process wherein the white oils, which normally resist further sulfonation, may be converted into sulfonic acids. We have found that these Whiteoils can be oxidized by blowing air or oxygenthrough them. The resulting oxidized product, may be then sulfonated easily with concentrated sulphuric acids, The sulpho-acids which are formed thereby are separated from the sulphuric acid and unchanged hydrocarbons in the usual The oxidation of the white oils is so re ulatedthat only a dehydrogenation ta es palace. While these white oils may be oxidized to obtain high molecular weight fatty acids, usually in the presence of catalysts and high pressures, we restrict our oxidation merely to a dehydrogenation of the oil. Therefore we carry out our oxidation process at comparatively low temperature, 140 to 180 C. being SllfiClGDt and under atmospheric pressure and in the absence'of catalysts. Furthermore, the oxidation must be stopped as soon as fatty acids begin to form. The quantity of fatty acids in the oxidized oil should not exceed 5 to 10%.

As stated, after the oil has been oxidized to dehydrogenate it, it is again'treated with sulphuric acid. v

Example 1 100 parts of a crude petroleum distillate, having a specific gravity of 0.898 and which has been purified with 50% of iriming sulphuric acid containing 20% sulphuric acld anhydride and subsequently washed, is treated with air at a temperature of 140 to150 C. until about 5% of fatty acids are formed. 100 parts of the thick, dark, yellow oil, resulting from-the oxidation is then sulfonated with 100 parts of concentrated sulphuric acid having a specific gravity of -1.82.- The sulfonation is carried out at a temperature'of about to C. and the sulphuric acid is slowly poured into the oil with rapid agitation.- The mixture is then allowed to stand and from it about 35% of sulfonic acid derivatives are obtained, 50% ofunchanged oil being separated ofi.

Example 2 ionic acids may be obtained when the oxidized hydrocarbon oil contains about 5% of fatty acids.

The sulfonic acids are extracted from the unchanged oil in the usual way, for instance, by treating with an alkaline solution, extraction with aqueous alcohol, etc. They may be' extracted in the form of salts of heavy metals insoluble in water or in various solvents such as benzine, petroleum, benzol, etc.

The remaining unchanged oil can again be oxidized and as described so that eventually all of the oil isconverted into sulfonic acids;

. The sulpho acids so obtained may be used in the hydrolysis of fats, as emulsifying agents, in the textile industries to wash wool,

etc.

What we claim is: 1. The rocess of preparing sulpho-aclds from cru e petroleum distillates no longer susceptible to sulfonation which comprises dehydrogenatingthe crude petroleum distillate by treatment with air and thereafter sulfonatmg the oil.

2. The process of preparing sulpho-acids from hydrocarbon oils no longer susceptible to sulfonation which comprises oxidizing the hydrocarbon oils by blowing air therethrough and thereafter sulfonating the oxidation product with stron sulphuric acid.

3. The processlot producing sulphp-acids 'from hydrocarbon oils no longer susceptible to sulfonation which comprises oxidizing the I oils by blowing air therethrough until a small separating sulpho compounds from the un-' amount of fatty acids are formed in'said oils and thereafter sulfonating the oxidation product.

4. The process of producing sulpho-acids from hydrocarbon oils no-longer susceptible to sulfonation which comprises oxidizing the hydrocarbon oils by blowing air therethrough, sulfonating the oxidation product,

changed hydrocarbons and again sulfonating the oxidation product. v

5. The process of preparing sulpho-acids from crude petroleum distillates which have been treated with strong sulphuric acid and no longer may be sulfonated, which comprises oxidizing the distillate by blowing air therethrough and thereafter sulfonating the oxidation product. 6. The process of preparing sulpho-acids from crude petroleum distillates which have been treated with sulphuric acids and may no longer be sulfonated which comprises oxidiz- I mg the distillate with air until about 5% of fatty acids are formed and thereafter s'ulfonating the oxidation product.

In testimony whereof we aifix our signatures.

GRIGORI PETROFF. PETER SHESTAKOFF. 

